CN102046310B - Method for producing soft magnetic material and method for producing dust core - Google Patents
Method for producing soft magnetic material and method for producing dust core Download PDFInfo
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- CN102046310B CN102046310B CN2009801191376A CN200980119137A CN102046310B CN 102046310 B CN102046310 B CN 102046310B CN 2009801191376 A CN2009801191376 A CN 2009801191376A CN 200980119137 A CN200980119137 A CN 200980119137A CN 102046310 B CN102046310 B CN 102046310B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0206—Manufacturing of magnetic cores by mechanical means
- H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/108—Mixtures obtained by warm mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
- H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
- H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
- H01F1/26—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated by macromolecular organic substances
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
Abstract
Disclosed is a method for efficiently producing a soft magnetic material which comprises a plurality of insulating layers on the surface of a soft magnetic metal particle. Specifically, a soft magnetic material serving as a material for a dust core is produced by: a step of preparing a material powder which is composed of composite magnetic particles, each obtained by forming an insulating coating film having hydrated water on the surface of a soft magnetic metal particle; a step of preparing a resin material containing a silicone which is cured by a hydrolysis-polycondensation reaction; and a step of forming a silicone coating film on the surface of the insulating coating film by mixing the material powder and the resin material in a heating atmosphere of 80-150 DEG C.
Description
Technical field
The present invention relates to make as the method for the soft magnetic material of dust core material and the method for making the dust core that uses this soft magnetic material and form.
Background technology
Hybrid vehicles etc. are used for being provided with booster circuit to the system of engine supply electric power at it.This booster circuit comprises that reactor is as parts.This reactor has wherein, and coil is wrapped in such structure on every side unshakable in one's determination.When using this reactor in alternating magnetic field, described meeting unshakable in one's determination produces the energy loss that is called as core loss.Usually, described core loss represents with magnetic hystersis loss and eddy-current loss sum, and it becomes especially obvious when using under high-frequency.
In order to reduce above-mentioned core loss, sometimes by using dust core to form the iron core of reactor.In order to form dust core, at first, the soft magnetic material that preparation is made of composite magnetic particle, wherein said composite magnetic particle is made of the soft magnetic metal particle that is coated with dielectric film.Then, the soft magnetic material compacting is formed dust core.Insulated from each other because metallic particles has dielectric film, thereby described dust core is particularly very effective to reducing eddy-current loss.
Though carried out above description, because dust core makes by compression moulding, so the pressure during compression moulding may destroy the dielectric film of composite magnetic particle.When dielectric film was damaged, the soft magnetic metal particle in the dust core came in contact each other.This contact can cause eddy-current loss to increase, thereby may reduce the high frequency characteristics of dust core.
In addition, strain and the dislocation that is incorporated in the compression moulding process in the soft magnetic metal particle can cause magnetic hystersis loss to increase.In order to prevent that magnetic hystersis loss from increasing, and must heat-treat after compression moulding.Yet this heat treatment may make the dielectric film deterioration, and it is disadvantageous therefore at high temperature heat-treating.If heat treatment temperature is not high enough, then can not remove strain that is incorporated in the metallic particles etc. fully.As a result, magnetic hystersis loss may increase, thereby reduces the high frequency characteristics of dust core.
In order to solve the problem that is caused by compression moulding and heat treatment; for example; such technology has been described in patent documentation 1: form the insulating barrier of multilayer on the surface of each soft magnetic metal particle, this insulating barrier by dielectric film, give stable on heating diaphragm and flexible diaphragm constitutes.According to the technology described in the document, described dielectric film can be formed by phosphorus-containing compound, silicon-containing compound etc., describedly give stable on heating diaphragm and can be formed by organo-silicon compound etc., and described flexible diaphragm can be formed by silicon etc.
The prior art document
Patent documentation
Patent documentation 1: disclosed Japanese Patent Application Laid-Open 2006-202956
Summary of the invention
Technical problem
Though carried out foregoing description, above-mentioned technology exists such problem: form the step complexity of the multilayer that is made of a plurality of insulating barriers on the surface of each soft magnetic metal particle, so the productivity ratio of soft magnetic material is low.
When forming a plurality of insulating barrier, fundamental method is to form insulating barrier on the surface of each soft magnetic metal particle continuously.For example, the technology described in the patent documentation 1 shows the wet type rubbing method as the method that forms insulating barrier.In the wet type rubbing method, at first, thing to be coated with is immersed in the organic solvent that is dissolved with insulating materials.This is waited to be coated with thing stirring and evaporation organic solvent.Then, described insulating materials is solidified, to wait that the surface that is coated with thing forms dielectric film.That is to say that the formation of dielectric film needs to stir, evaporate and solidify this 3 steps.Therefore, the productivity ratio of soft magnetic material is lower.
In addition, for example, when selecting the organosilicon membrane conduct to be formed on the insulating barrier of waiting to be coated with on the thing, can adopt following method.At first, will wait to be coated with thing with blender mixes with organosilicon.Then, under heating atmosphere, promote organosilyl polycondensation.Waiting that the surface that is coated with thing forms described organosilicon membrane thus.In this case, all steps are reduced to mixing and these 2 steps of heat treatment of material.Yet, consider on the surface of each soft magnetic metal particle to form a plurality of insulating barriers that the step that can be described as this method is still a lot.
In view of the foregoing, in order to suppress by compression moulding and heat treatment and the reduction of the magnetic characteristic that causes, an object of the present invention is to provide a kind of method of making soft magnetic material, this method can be made the soft magnetic material that is made of the soft magnetic metal particle effectively, and wherein said soft magnetic metal particle is coated with a plurality of insulating barriers.
Another object of the present invention provides a kind of method of making dust core, and this method can be used for making the dust core with excellent high frequency characteristics.
The method of dealing with problems
The inventor has paid close attention to two insulating barriers adjacent one another are on thickness direction on each soft magnetic metal particle surface, and finds can realize above-mentioned purpose by the structure that limits these two insulating barriers.Based on this discovery, the present invention is specific as follows.
The method of manufacturing soft magnetic material of the present invention is the method for making for the preparation of the soft magnetic material of dust core, and this method comprises the steps:
(a) preparation has the step of the material powder of composite magnetic particle, and described composite magnetic particle has:
(a1) soft magnetic metal particle; And
(a2) dielectric film, this dielectric film contain hydrate water and are formed on the surface of each described soft magnetic metal particle (being called steps A hereinafter);
(b) preparation contains the step of organosilyl resin material, and described organosilicon solidifies (being called step B hereinafter) by hydrolysis-condensation reaction; And
(c) under 80 ℃ to 150 ℃ heating atmosphere, mix described material powder and described resin material, to form the step (being called step C hereinafter) of organosilicon membrane on the surface of described dielectric film.
Method according to manufacturing soft magnetic material of the present invention, can make the soft magnetic material that is constituted by composite magnetic particle at short notice effectively, wherein said composite magnetic particle is made of the soft magnetic metal particle that is coated with a plurality of insulating barriers, and described insulating barrier is formed by dielectric film and organosilicon membrane.The reason that can make soft magnetic material effectively is that the hydrate water that contains in the dielectric film can promote the formation of organosilicon membrane.Detailed mechanism will be described below.
The method of manufacturing dust core of the present invention comprises the steps:
(a) step (being called step D hereinafter) of the soft magnetic material compression moulding that will make by the method for above-mentioned manufacturing soft magnetic material; And
(b) heat-treat, to remove the step (being called step e hereinafter) that in the compression moulding process, is incorporated into the strain in the soft magnetic metal particle.
According to the method for manufacturing dust core of the present invention, after with soft magnetic material compression moulding of the present invention, carry out high-temperature heat treatment.Therefore, can remove strain and dislocation in the metallic particles that in pressing process, is incorporated into soft magnetic material fully.Because soft magnetic material is made of composite magnetic particle, and this composite magnetic particle is made of the soft magnetic metal particle that is coated with a plurality of insulating barriers, thereby after compacting, can at high temperature heat-treat this soft magnetic material.The dust core that strain etc. have fully been removed has excellent efficiency owing to core loss reduces.The dust core that said method obtains can be suitable as the iron core of (for example) reactor.
Inscape to each step in the method for manufacturing soft magnetic material of the present invention and dust core is described in detail below.
Steps A: the preparation of material powder
The material powder for preparing is by form the aggregation of the composite magnetic particle that the dielectric film that contains hydrate water makes on the surface of each soft magnetic metal particle.
Preferably, the soft magnetic metal particle contains 50 quality % or more iron.The kind of metallic particles material (for example) comprises pure iron (Fe).In addition, can also use following ferroalloy, for example: Fe-Si is that alloy, Fe-Al are that alloy, Fe-N are that alloy, Fe-Ni are that alloy, Fe-C are that alloy, Fe-B are that alloy, Fe-Co are that alloy, Fe-P are that alloy, Fe-Ni-Co are that alloy and Fe-Al-Si are alloy.Particularly, consider the preferred pure iron with 99 quality % or more iron that uses from the angle of magnetic conductivity and magnetic flux density.
The average grain diameter that the present invention has stipulated the soft magnetic metal particle is more than or equal to 1 μ m and be less than or equal to 70 μ m.When the average grain diameter of described soft magnetic metal particle during more than or equal to 1 μ m, this feature can suppress to use the magnetic coercive force of the dust core that soft magnetic material makes and the increase of magnetic hystersis loss, and can not reduce the flowability of soft magnetic material.On the other hand, when the average grain diameter of soft magnetic metal particle was less than or equal to 70 μ m, this feature can effectively reduce the eddy-current loss that occurs in the above high frequency region of 1kHz.More preferably, the average grain diameter of soft magnetic metal particle is more than or equal to 50 μ m and be less than or equal to 70 μ m.When the lower limit of average grain diameter during more than or equal to 50 μ m, not only can obtain effect that eddy-current loss is reduced, the processing of soft magnetic material is become easily, thereby can obtain to have the formed body of higher density.In the above description, term " average grain diameter " refers to: in the histogram of particle diameter, from the minimum side of particle diameter, the quality sum of particle reaches 50% o'clock particle diameter of particle gross mass, that is, and and 50% particle diameter.
Preferably, all to have draw ratio be 1.5 to 1.8 shape to the soft magnetic metal particle.Compare with the soft magnetic metal particle with less draw ratio (close to 1.0), the soft magnetic metal particle of draw ratio in above-mentioned scope can form the dust core that demagnetization factor is bigger thereby high frequency characteristics is excellent.In addition, the intensity of dust core is increased.
The dielectric film that coats each soft magnetic metal particle surface plays insulating barrier between metallic particles.By coat each metallic particles with dielectric film, can suppress metallic particles and contact each other, thereby the relative permeability of formed body can be reduced to than low value.In addition, the existence of dielectric film can suppress eddy current flow through metallic particles, thereby reduces the eddy-current loss of dust core.
Described dielectric film is not particularly limited, as long as it contains hydrate water and has excellent insulating properties.For example, can suitably form described dielectric film by using phosphate or titanate.Particularly, the dielectric film of being made by phosphate has excellent deformability.Therefore, when soft magnetic material made dust core, even the soft magnetic metal particle deforms, dielectric film also can be out of shape along with the distortion of metallic particles.And, the ability height that phosphate layer and iron-base soft magnetic metallic particles closely contact, thereby described film is not easy to come off from the surface of metallic particles.As phosphate, can use following metal phosphate compounds: ferric phosphate, manganese phosphate, trbasic zinc phosphate and calcium phosphate.Can form the dielectric film that contains hydrate water by the material that use contains hydrate water.
Preferably, the thickness of dielectric film is more than or equal to 10nm and be less than or equal to 1 μ m.When the thickness of dielectric film during more than or equal to 10nm, can suppress metallic particles and contact with each other, and can effectively suppress the energy loss that caused by eddy current.When the thickness of dielectric film was less than or equal to 1 μ m, the dielectric film ratio in the composite magnetic particle can be not excessive.This feature can prevent the remarkable reduction of the magnetic flux density in the composite magnetic particle.
Above-mentioned insulator film thickness can detect by following method.At first, the film that use obtains by composition analysis (transmission electron microscope-energy dispersion type x-ray spectrometry (TEM-EDX)) is formed and is calculated by the amount of element that inductivity coupled plasma mass spectrometry (ICP-MS) obtains, thereby draws thickness.Then, utilize the TEM photo directly to observe and film to confirm that the order of magnitude by calculating the thickness that draws in advance is suitable value.This definition also can be applicable to the thickness of following organosilicon membrane.
Step B: the preparation of resin material
Be not particularly limited for the resin material that will prepare, as long as this material is the organosilicon that can solidify by hydrolysis-condensation reaction.Usually, can use by Si
m(OR)
nThe compound of (herein, m and n are natural number) expression.OR represents hydrolyzable groups in the chemical expression.The kind of hydrolyzable groups comprises alkoxyl, acetoxyl group, halogen group, NCO and hydroxyl.Particularly, as described resin material, can suitably use the alkoxyl oligomer of molecular end alkoxy silicyl (≡ Si-OR) sealing.The kind of alkoxyl comprises methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, sec-butoxy and tert-butoxy.Particularly, consider the required time and efforts of product of removing after the hydrolysis, hydrolyzable groups is preferably methoxyl group.These resin materials can be used singly or in combination.
The organosilicon membrane that hydrolysis and polycondensation by resin material forms has excellent deformability.Therefore, in the process of compacting soft magnetic material, be not easy in the organosilicon membrane to produce and break and crackle.The situation that organosilicon membrane is peeled off from the dielectric film surface can take place hardly.In addition, organosilicon membrane has excellent hear resistance, and therefore, even when heat-treating under high temperature after with soft magnetic material compression moulding, this organosilicon membrane also can be kept excellent insulating properties.
Step C: the mixing of material powder and resin material
Under 80 ℃ to 150 ℃ heating atmosphere, mix described material powder and resin material.By mixing, the surface that has produced each composite magnetic particle is coated with the state of resin material.At this moment, because heating atmosphere, the hydrate water that contains in the dielectric film of composite magnetic particle decomposes, thereby promotes the hydrolysis of resin material.Hydrate water begins to decompose under about 80 ℃.Along with temperature raises, decomposition rate increases, thereby promotes the hydrolysis-condensation reaction of resin material.Therefore, preferably, make heating atmosphere maintain 100 ℃ to 150 ℃.High temperature can be conducive to remove the organic matter (for example, be under the situation of methoxyl group at hydrolyzable groups, described organic matter is methyl alcohol) that produces when hydrolysis and polycondensation.
, after material is mixed, heat-treated in the past, and use the hydrone that contains in the heating atmosphere to promote hydrolysis and the polycondensation of resin material.Yet, in the method for manufacturing soft magnetic material of the present invention, owing to generate the below that the dielectric film of originating is located immediately at resin material as hydrone, thereby in the very short time, promote hydrolysis and the polycondensation of resin material.For example, under the situation of using the XC96-B0446 that is made by GE Toshiba Silicone Co., Ltd., in the past, (this condition is recommended by the resin manufacture merchant) more than 60 minutes carried out in the heat treatment after mixing under 150 ℃.In contrast be, in the method for the invention, can be 80 ℃ to 150 ℃ down heating about 10 minutes to 30 minutes.In addition and since the generation of hydrone source be positioned at resin material near, even thereby mix in enormous quantities with tens feather weight, also can be reliably the resin material on coated insulation film surface be changed into organosilicon membrane.
In order to satisfy the desirable characteristics of dust core to be manufactured, can suitably select to prepare the ratio of material powder and resin material.Particularly, improve in hope under the situation of dc superposition characteristic, preferably, the ratio of resin material during mixing (, resin material shared ratio in the total amount of material powder and resin material) and be 0.5 quality % to 2.5 quality %.When the ratio of resin material dropped in the scope of 0.5 quality % to 2.5 quality %, the whole surface of each composite magnetic particle can be coated by organosilicon membrane in fact.Thus, can improve insulating properties between the soft magnetic metal particle.In addition, compare with the thickness of routine, the thickness of formed organosilicon membrane is increased.Therefore, when making following dust core, can improve the heat treatment temperature after the compression moulding.
The above-mentioned preferred proportion of resin material is greater than the resin material ratio in the method for traditional manufacturing soft magnetic material (about 0.25 quality %) (mixing and heat treatment are carried out respectively) in the past.Can make resin material the reason that increases of mixed proportion be, by under heating atmosphere, mixing the hydrolysis-condensation reaction that can promote resin material, and (for example can easily remove the organic matter that the time produces in reaction, be under the situation of methoxyl group at hydrolyzable groups, described organic matter is methyl alcohol).
Preferably, the thickness of organosilicon membrane is 10nm to 0.2 μ m.When the thickness of organic silicon fiml is in this scope, can guarantees the insulating properties between the soft magnetic metal particle, and can exceedingly not reduce magnetic flux density.
In order in blend step, to promote the formation of organosilicon membrane, can add catalyst.The kind of spendable catalyst comprises organic acid, for example formic acid, maleic acid, fumaric acid and acetic acid; And inorganic acid, for example hydrochloric acid, phosphoric acid, nitric acid, boric acid and sulfuric acid.Because excessive catalyst can cause the gelation of resin material, the therefore suitable addition of selecting catalyst preferably.
In the soft magnetic material of as above manufacturing, the surface of each soft magnetic metal particle is coated with dielectric film and organosilicon membrane.Therefore, though in step D subsequently with soft magnetic material compression moulding, the soft magnetic metal particle also can be in direct contact with one another hardly.Because organosilicon membrane is formed on the surface of each composite magnetic particle, even heat-treat, also can suppress dielectric film generation thermal decomposition in step e subsequently, thereby can prevent the contact between the soft magnetic metal particle effectively under high temperature.
Inventor research has also proved: compare with traditional soft magnetic material (its heat-treat after mixing and obtain), with soft magnetic material of the present invention (its when material powder and resin material are mixed, heat-treat and obtain) when being used for dust core, even the ratio of resin material is identical when mixing, soft magnetic material of the present invention also has more excellent magnetic characteristic.The possible cause that produces this phenomenon is, owing to when material powder and resin material are mixed, form organosilicon membrane by heat treatment, thereby form the organosilicon membrane of the relative homogeneous of thickness.
Step D: compression moulding
Usually, can be by the following process step that is pressed: the soft magnetic material that obtains among the step C is put in the mould with regulation shape, by exerting pressure it is suppressed then.Can suitably select the pressure of this operation.Yet, for example, being used as in manufacturing under the situation of dust core of iron core of reactor, pressure is preferably about 900MPa to 1,300MPa, 960MPa to 1 more preferably, 280MPa.
Step e: heat treatment
Heat-treat is in order to remove the strain that is incorporated in the soft magnetic metal particle, dislocation etc. in step D.Along with heat treatment temperature raises, the effect of removing of strain increases.Therefore, preferably 400 ℃ or higher, particularly preferably in 550 ℃ or higher, further preferably under 650 ℃ or higher temperature, heat-treat.The angle of the strain from remove metallic particles etc. is considered, is limited to about 800 ℃ on the regulation heat treatment temperature of the present invention.Adopt above-mentioned heat treatment temperature, not only can remove the strain that when compacting, is incorporated in the metallic particles, and can remove lattice defect (for example dislocation).The reason of the heat treatment temperature that can raise is that soft magnetic material of the present invention has the higher organosilicon membrane of hear resistance.Owing to adopt high heat treatment temperature can fully remove strain and the dislocation that is incorporated in the soft magnetic metal particle, thereby can effectively reduce the magnetic hystersis loss of dust core.
The invention effect
Adopt the method for manufacturing soft magnetic material of the present invention, can have the soft magnetic material of soft magnetic metal particle (it is coated with dielectric film and organosilicon membrane) with the high production rate manufacturing.Because the soft magnetic material of manufacturing has the soft magnetic metal particle that the surface all is coated with dielectric film and organosilicon membrane, therefore, when heat-treating when compression moulding, after compression moulding, overlay film is not easy destroyed, so their insulating properties also is not easy to reduce.
In addition, according to the method for manufacturing dust core of the present invention, after compression moulding, carry out high-temperature heat treatment, can make the dust core that strain etc. has fully been removed.When using under high frequency condition, the energy loss of dust core that does not contain strain etc. is lower.Can demonstrate excellent characteristic when therefore, this dust core (for example) is as reactor unshakable in one's determination.When using dust core (for example) as reactor unshakable in one's determination, because this dust core has excellent dc superposition characteristic, therefore can realize not having the gap iron core.
Brief Description Of Drawings
Fig. 1 is the figure of the method for explanation test dc superposition characteristic.
Fig. 2 is the figure that the dc superposition characteristic test result is shown, and wherein, transverse axis is represented the DC current (A) that superposes, and the longitudinal axis is represented inductance (μ H).
Fig. 3 is the figure that dc superposition characteristic is shown, and wherein, transverse axis is represented the magnetic field (Oe) that applies, and the longitudinal axis is represented differential permeability.
Embodiment of the present invention
Make dust core (trial-production material 1 and trial-production material 2) by the method for manufacturing dust core of the present invention, to measure their physical characteristic, described method comprises that following step (A) is to (E).In addition, make dust core (contrast material) by the method for traditional manufacturing dust core, to measure their physical characteristic.The physical characteristic of trial-production material 1, trial-production material 2 and contrast material is compared.
The manufacturing of trial-production material 1
(A) step of the material powder that is made of composite magnetic particle of preparation, wherein said composite magnetic particle is to form the dielectric film that contains hydrate water by the surface at each soft magnetic metal particle to make.
(B) preparation contains the step of organosilyl resin material, and wherein said organosilicon solidifies by hydrolysis-condensation reaction in the presence of water.
(C) under 80 ℃ to 150 ℃ heating atmosphere, mix described material powder and resin material to form the step of organosilicon membrane on the surface of dielectric film.
(D) step of the soft magnetic material compression moulding that will be made of the soft magnetic metal particle, wherein said soft magnetic metal particle is coated with dielectric film and organosilicon membrane.
(E) heat-treat to remove the step that in the compression moulding process, is incorporated into the strain in the soft magnetic metal particle.
Steps A
(average grain diameter: 50 μ m, draw ratio: 1.51) as the soft magnetic metal particle, this iron powder is made by water atomization technology, and the purity of this iron powder is more than 99.8% to prepare erose iron powder.The phosphate chemical conversion processing is carried out on surface to metallic particles, thereby forms the dielectric film that is made of ferric phosphate contain hydrate water.Make composite magnetic particle thus.The almost whole surface of each soft magnetic metal particle all is insulated film and coats.The average thickness of dielectric film is 50nm.During the hydrate water that contains in by thermal decomposition spectrographic determination dielectric film, its content is 7.78 quality %.The aggregation of composite magnetic particle is the material powder for the manufacture of soft magnetic material.
Step B
As the organosilyl resin material that contains that solidifies by hydrolysis-condensation reaction, prepared TSR116 and XC96-B0446, these two is all made by GE Toshiba Silicone Co., Ltd..They are alkoxyl resin type organosilicon oligomer of molecular end alkoxy silicyl (≡ Si-OR) sealing, and hydrolyzable groups (R) is methoxyl group.The order of determining step A and step B suitably.
Step C
The resin material (TSR116 and XC96-B0446) that material powder prepared in the steps A and step B prepare is put into blender.They were mixed 10 minutes under 150 ℃ heating atmosphere, thereby obtain soft magnetic material.In the material in putting into blender, the ratio of TSR116 is 0.75 quality %, and the ratio of XC96-B0446 is 0.5 quality %.The rotating speed of described blender is 300rpm.
Step C makes such soft magnetic material, and wherein each composite magnetic particle is coated with organosilicon membrane.The average thickness that is formed on the lip-deep organosilicon membrane of composite magnetic particle is 200nm.
Step D
The soft magnetic material that obtains among the step C is put in the mould with regulation shape.Under the pressure of 960MPa, soft magnetic material is pressed, thereby makes bar-shaped sample and ring-shaped sample.The size of sample is as follows:
Bar-shaped sample: be used for estimating dc superposition characteristic
Length: 55mm; Width: 10mm; Thickness: 7.5mm
Ring-shaped sample: be used for estimating magnetic characteristic
External diameter: 34mm; Internal diameter: 20mm; Thickness: 5mm
Step e
Under nitrogen atmosphere, under 600 ℃, the bar-shaped sample and the ring-shaped sample that obtain among the step D were heat-treated 1 hour.Be so-called dust core through heat treated sample.
The manufacturing of trial-production material 2
Trial-production material 2 is as described below with the difference of trial-production material 1.In step C, the ratio of resin material is 0.25 quality % (TSR116 is identical with the ratio of XC96-B0446 with trial-production material 1).In this case, the average thickness of organosilicon membrane is 100nm.
Identical with trial-production material 1, made bar-shaped sample and ring-shaped sample with trial-production material 2, to measure dc superposition characteristic and magnetic characteristic.
The manufacturing of contrast material
Contrast material is as described below with the difference of trial-production material 1.
1. in step C, the ratio of resin material is 0.25 quality % (TSR116 is identical with the ratio of XC96-B0446 with trial-production material 1).In this case, the average thickness of organosilicon membrane is 100nm.
2. after material powder and resin material are mixed 10 minutes, in 150 ℃ of following heat treatments 60 minutes, thereby form organosilicon membrane.In other words, though the amount of the resin material that will solidify is less, makes the 1 used total time of prepared material of having a competition total time of soft magnetic material in the contrast material and grow 60 minutes.Can predict, when the amount of the soft magnetic material that will make increased, it is more obvious that the difference of manufacturing time becomes.
Identical with trial-production material 1 and 2, made bar-shaped sample and ring-shaped sample with contrast material, to measure dc superposition characteristic and magnetic characteristic.
Estimate
To according to the trial-production material 1 of said method manufacturing and 2 and the following characteristic of contrast material measure.The characteristic of measuring is summarised among Table I described later and the II.
Magnetic characteristic
Bar-shaped sample is applied 100 Oe (≒ 7, and magnetic field 958A/m) is to measure magnetic flux density B
100
Coil is arranged on the ring-shaped sample, to be formed for measuring the measurement sample of sample magnetic characteristic.For described measurement sample, exciting flux density (Bm) be 1kG (=0.1T), measuring frequency is to carry out the measurement of core loss W1/10k (W/kg) under the condition of 10kHz, and exciting flux density (Bm) be 2kG (=0.2T), measuring frequency is to carry out the measurement of core loss W2/10k (W/kg) under the condition of 10kHz.Use the AC-BH tracer to carry out described measurement.In addition, utilize least square method, based on the frequency curve of three formula match core loss shown in following, thereby calculate hysteresis loss coefficient Kh (mWs/kg) and eddy current loss factor Ke (mWs
2/ kg).
(core loss)=(magnetic hystersis loss)+(eddy-current loss)
(magnetic hystersis loss)=(hysteresis loss coefficient) * (frequency)
(eddy-current loss)=(eddy current loss factor) * (frequency)
2
Described measurement sample also is used for measuring initial permeability μ i (H/m).Use DC/AC-BH tracer (being made by METRON company) to measure described initial permeability.
Density
Measure the submergence density (g/cm of bar-shaped sample and ring-shaped sample
3).Measurement result has confirmed that the density of two kinds of samples is identical.
Resistance
Measure the resistance (Ω) of ring-shaped sample by four-terminal method.
Dc superposition characteristic
As shown in Figure 1, will be combined with spacer S by the M unshakable in one's determination that bar-shaped sample constitutes, and with coil C be wrapped in M unshakable in one's determination around.Make thus for the test suite of measuring dc superposition characteristic.In test suite, the number of turn of coil is 54, and the length of magnetic path is 220mm, and the magnetic circuit sectional area is 75mm
2In test suite, the gross thickness by change spacer S can change the gap length that is present among the M unshakable in one's determination.In this test, adopt 0mm, 0.6mm, 1.2mm, 2.0mm, 2.8mm and these different gap lengths of 4.0mm, and change to 40.0A for each gap length DC current that will superpose from 0A, thereby measure the inductance value L (μ H) of the test suite that is combined with the M unshakable in one's determination that is formed by trial-production material 1.In addition, adopt the gap length of 2.0mm, and the DC current that will superpose changes into 40.0A from 0A, thereby measurement is combined with the inductance value L (μ H) of the test suite of the M unshakable in one's determination that is formed by contrast material.
Fig. 2 is the figure that the measured value of the inductance value of test suite (trial-production material 1 and contrast material) for each stack DC current is shown.When the stack DC current increases, if inductance value L is that the amplitude that the inductance value L of 0 ampere-hour begins to reduce is talked about more significantly from superimposed current, then be rated this dc superposition characteristic relatively poor.
In addition, in order to estimate the difference of the dc superposition characteristic between each specimen more clearly, measured the differential permeability (Δ B/ Δ H) of each specimen.This differential permeability obtains by following method.At first, by the ring-shaped sample to each specimen coil is set, measures sample thereby form.Be under the condition of 100 Oe in the magnetic field that applies, the dc magnetizing characteristic of measuring sample is measured.Based on this measured value, calculate described differential permeability.Fig. 3 shows the magnetic field that applies and the relation between the differential permeability for trial-production material 1, trial-production material 2 and contrast material.In this case, when the difference of the maximum of differential permeability and minimum of a value more hour, dc superposition characteristic is more good.
Table I
Table II
Evaluation result
From the result shown in Table I and the II as seen, since trial-production material 1 and 2 and contrast material in, guaranteed the insulating properties between the composite magnetic particle, so its hysteresis loss coefficient Kh and eddy current loss factor Ke are less, thereby core loss is suppressed to than low value.Because trial-production material 2 has the dielectric film and organosilicon membrane (thickness of this dielectric film and the organosilicon membrane all respective thickness with contrast material is identical) that is made of ferric phosphate, thereby it has the characteristic suitable with contrast material.On the other hand, because the organosilicon membrane thickness comparison of trial-production material 1 is bigger than the respective thickness of material, thereby compare its B with contrast material
100Lower with μ i, and core loss value etc. is higher.Trial-production material 1 and 2 and the value of contrast material be much better than by on the surface of each soft magnetic metal particle, only forming those materials (not shown data) that phosphate layer is made.In other words, we can say to have excellent high frequency characteristics by the dust core that uses the soft magnetic material that constituted by the soft magnetic metal particle that is coated with phosphate layer and organosilicon membrane to make.
From result shown in Figure 2 as seen, when superimposed current is changed into 40.0A from 0A, compare with contrast material, the reduction amplitude of inductance value is less in the trial-production material 1.This result has confirmed that trial-production material 1 has excellent dc superposition characteristic.Possible reason is and since the organosilicon membrane comparison of trial-production material 1 than the organosilicon membrane of material thicker and homogeneous more, thereby compare with contrast material, the resistivity of trial-production material 1 is bigger, and magnetic conductivity is littler.Therefore, when use has dust core manufacturing by the structure that forms of trial-production material 1 when being used for reactor unshakable in one's determination, can omit the gap for the adjusting inductance value.
From result shown in Figure 3 as seen, though the resin material addition of trial-production material 2 and contrast material is identical, compare with contrast material, the dc superposition characteristic of the inductance value of trial-production material 2 is more stable.Because the difference of trial-production material 2 and contrast material only is to form the method for organosilicon membrane, so this result shows that with regard to the dc superposition characteristic that improves soft magnetic material, the method for manufacturing soft magnetic material of the present invention is better than traditional method.This result also shows, the dc superposition characteristic of trial-production material 1 (wherein, the resin material ratio among the step C is 1.25 quality %) and this ratio wherein are that the trial-production material 2 of 0.25 quality % is compared better.
Embodiment of the present invention are not limited to above-mentioned embodiment, in the scope that does not break away from main points of the present invention, can carry out suitable modification to them.
Industrial applicibility
The soft magnetic material of the method manufacturing by manufacturing soft magnetic material of the present invention has excellent high frequency characteristics and the dust core of dc superposition characteristic applicable to manufacturing.
Reference symbol
M: iron core; C: coil; S: spacer
Claims (6)
1. manufacture method for the manufacture of the soft magnetic material of dust core, this method comprises the steps:
(a) preparation comprises the material powder of composite magnetic particle, and described composite magnetic particle comprises:
(a1) soft magnetic metal particle; And
(a2) dielectric film, this dielectric film contain hydrate water and are formed on the surface of each described soft magnetic metal particle;
(b) preparation contains organosilyl resin material, and described organosilicon solidifies by hydrolysis-condensation reaction; And
(c) under 80 ℃ to 150 ℃ heating atmosphere, mix described material powder and described resin material, form organosilicon membrane with the surface at described dielectric film.
2. the manufacture method of soft magnetic material according to claim 1, wherein, in described blend step, the ratio of described resin material is 0.5 quality % to 2.5 quality %.
3. the manufacture method of soft magnetic material according to claim 1, wherein, the average grain diameter of described soft magnetic metal particle is for more than or equal to 1 μ m and be less than or equal to 70 μ m.
4. the manufacture method of soft magnetic material according to claim 1, wherein, the draw ratio of described soft magnetic metal particle is 1.5 to 1.8.
5. the manufacture method of soft magnetic material according to claim 1, wherein, described dielectric film is phosphate layer.
6. method of making dust core, this method comprises the steps:
(a) the soft magnetic material compression moulding that will make by the manufacture method of the described soft magnetic material of claim 1; And
(b) heat-treat, to remove the strain that in the compression moulding process, is incorporated in the described soft magnetic metal particle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-301637 | 2008-11-26 | ||
| JP2008301637A JP4513131B2 (en) | 2008-05-23 | 2008-11-26 | Method for producing soft magnetic material and method for producing dust core |
| PCT/JP2009/005635 WO2010061525A1 (en) | 2008-11-26 | 2009-10-26 | Method for producing soft magnetic material and method for producing dust core |
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| EP (1) | EP2359963B1 (en) |
| KR (1) | KR20110089237A (en) |
| CN (1) | CN102046310B (en) |
| WO (1) | WO2010061525A1 (en) |
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| JP5976284B2 (en) * | 2010-07-23 | 2016-08-23 | 株式会社豊田中央研究所 | Method for producing dust core and method for producing powder for magnetic core |
| JP5778993B2 (en) * | 2011-05-26 | 2015-09-16 | 住友電気工業株式会社 | Molding method of green compact |
| CN104217834B (en) * | 2013-06-03 | 2018-01-23 | 株式会社田村制作所 | Soft magnetic powder composition, core, reactor |
| JP6243298B2 (en) * | 2014-06-13 | 2017-12-06 | 株式会社豊田中央研究所 | Powder magnetic core and reactor |
| JP6443269B2 (en) * | 2015-09-01 | 2018-12-26 | 株式会社村田製作所 | Magnetic core and manufacturing method thereof |
| JP6378156B2 (en) * | 2015-10-14 | 2018-08-22 | トヨタ自動車株式会社 | Powder magnetic core, powder for powder magnetic core, and method for producing powder magnetic core |
| CN113692078A (en) * | 2021-07-08 | 2021-11-23 | 华南理工大学 | Curing system and method for magnetic composite material |
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- 2009-10-26 WO PCT/JP2009/005635 patent/WO2010061525A1/en active Application Filing
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Also Published As
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| CN102046310A (en) | 2011-05-04 |
| KR20110089237A (en) | 2011-08-05 |
| EP2359963A4 (en) | 2016-08-31 |
| EP2359963A1 (en) | 2011-08-24 |
| EP2359963B1 (en) | 2017-09-06 |
| WO2010061525A1 (en) | 2010-06-03 |
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